# US 2014/0193322 A1 · Rigid foams based on procyanidin- and/or prodelphinidin-type tannins and preparation method thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0193322 A1 - Document ID: US20140193322A1 - Status: Published application - Kind: A1 - Application number: 14/240,724 - Filed: 2012-08-02 - Published: 2014-07-10 - Earliest claimed: 2011-08-23 - Assignees: Centre National De La Recherche Scientifique; Universite De Lorraine - Inventors: Alain Celzard; Maria-Cecilia Basso; Antonio Pizzi; Vanessa Fierro - Web page: https://patentgrep.com/patent/US20140193322A1 ## CPC - C08G 65/38: derived from phenols - C01B 32/382: {Making shaped products, e.g. fibres, spheres, membranes or foam} - C08J 9/0023: {containing oxygen} - C08J 9/0033: {containing sulfur} - C08J 9/142: {Compounds containing oxygen but no halogen atom} - C08J 2361/06: of aldehydes with phenols - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) ## Abstract Use of at least one procyanidin- and/or prodelphinidin-type tannin, devoid of prorobinetidin- and/or profisetinidin-type tannin, in a mixture with furfuryl alcohol for the implementation of a polymerization reaction for the preparation of rigid foams, said procyanidin- and/or prodelphinidin-type tannin being in particular pine bark tannin. ## Claims ### Claim 1 Use of at least one procyanidin- and/or prodelphinidin-type tannin, devoid of prorobinetidin- and/or profisetinidin-type tannin, in a mixture with furfuryl alcohol for the implementation of a polymerization reaction for the preparation of rigid foams, said procyanidin- and/or prodelphinidin-type tannin being in particular pine bark tannin. ### Claim 2 (depends on 1) Use according to claim 1, in which said tannin-furfuryl alcohol mixture is devoid of formaldehyde. ### Claim 3 (depends on 1) Use according to claim 1, in which said tannin-furfuryl alcohol mixture comprises formaldehyde. ### Claim 4 (depends on 1, 2, 3) Use according to one of claims 1 to 3, comprising moreover a volatile solvent, in particular diethyl ether, a catalyst, in particular paratoluenesulphonic acid, and optionally one or more additives. ### Claim 5 Rigid foam comprising at least one procyanidin- and/or prodelphinidin-type tannin, polymerized with furfuryl alcohol and devoid of prorobinetidin- and/or profisetinidin-type tannin polymerized with furfuryl alcohol, said tannin being in particular pine bark tannin. ### Claim 6 (depends on 5) Rigid foam according to claim 5, devoid of the polycondensation products of formaldehyde with said procyanidin- and/or prodelphinidin-type tannin. ### Claim 7 (depends on 6) Rigid foam according to claim 6, having an apparent density comprised from 0.01 g/cm3 to 0.16 g/cm3, in particular 0.02 g/cm3 to 0.025 g/cm3 and/or a thermal conductivity comprised from 0.03 W/m/K to 0.05 W/m/K, in particular 0.030 W/m/K and/or a modulus of elasticity comprised from 0.05 MPa to 14 MPa, in particular 0.1 MPa. ### Claim 8 (depends on 5) Rigid foam according to claim 5, comprising moreover the polycondensation products of formaldehyde with said procyanidin- and/or prodelphinidin-type tannin and devoid of the polycondensation products of formaldehyde with said prorobinetidin- and/or profisetinidin-type tannin. ### Claim 9 (depends on 8) Rigid foam according to claim 8, having an apparent density comprised from 0.01 g/cm3 to 0.20 g/cm3, particularly from 0.01 g/cm3 to 0.16 g/cm3, in particular 0.07 g/cm3 and/or a thermal conductivity comprised from 0.03 W/m/K to 0.06 W/m/K, particularly from 0.03 W/m/K to 0.05 W/m/K, in particular 0.039 W/m/K and/or a modulus of elasticity comprised from 0.16 MPa to 30 MPa, particularly from 0.16 MPa to 16 MPa, advantageously 2.5, in particular 1.49 MPa. ### Claim 10 (depends on 5, 6, 7, 8, 9) Rigid foam according to one of claims 5 to 9, comprising moreover one or more additives, in particular chosen from the group comprising a surfactant, boric acid, phosphoric acid, PEG and mixtures thereof. ### Claim 11 (depends on 5) Process for the preparation of a rigid foam as defined in claim 5, comprising from two to five steps of introduction of at least one procyanidin- and/or prodelphinidin-type tannin, devoid of prorobinetidin- and/or profisetinidin-type tannin, with furfuryl alcohol. ### Claim 12 (depends on 11) Process for the preparation of a rigid foam according to claim 11, in which said steps of bringing at least one procyanidin- and/or prodelphinidin-type tannin into contact with furfuryl alcohol are carried out in the presence of a volatile solvent, in particular diethyl ether, and optionally of additives, in a time of less than 30 minutes, preferentially less than 20 minutes and more preferentially less than 10 minutes. ### Claim 13 (depends on 11, 12) Process for the preparation of a rigid foam according to claim 11 or 12, comprising moreover a step of the addition of a catalyst, in particular of paratoluenesulphonic acid. ### Claim 14 (depends on 11, 12, 13) Process for the preparation of a rigid foam according to one of claims 11 to 13, comprising the following steps: a. Contacting a fraction by weight of the total quantity of at least one procyanidin- and/or prodelphinidin-type tannin, devoid of prorobinetidin- and/or profisetinidin-type tannin to be implemented, in particular 1/3, in a mixture comprising furfuryl alcohol, diethyl ether and optionally additives, b. Stirring the mixture of step a. c. Introduction of a second fraction by weight equivalent to that of step a. and stirring. d. Introduction of a third fraction by weight equivalent to that of step a. and stirring. e. Stirring the mixture comprising the total quantity of tannin, furfuryl alcohol, diethyl ether and optionally additives for a time that ensures the homogeneity of the mixture. f. The optional addition of other additives to this mixture and stirring until homogenization is complete. g. Addition to the mixture comprising the total quantity of tannin, of a catalyst, in particular paratoluenesulphonic acid. h. Stirring the mixture comprising the total quantity of tannin, furfuryl alcohol, diethyl ether, optionally additives and the catalyst at a speed equivalent to that of step c for a time that ensures the homogeneity of the mixture. ### Claim 15 (depends on 11, 12, 13) Process according to one of claims 11 to 13, comprising the following steps: a. Introduction of a fraction by weight of the total quantity of at least one procyanidin- and/or prodelphinidin-type tannin, devoid of prorobinetidin- and/or profisetinidin-type tannin to be implemented, in particular 1/3, in a mixture comprising furfuryl alcohol, diethyl ether, formaldehyde and optionally additives, b. Stirring the mixture of step a. c. Introduction of a second fraction by weight equivalent to that of step a. and stirring. d. Introduction of a third fraction by weight equivalent to that of step a. and stirring. e. Stirring the mixture comprising the total quantity of tannin, furfuryl alcohol, diethyl ether, formaldehyde and optionally additives for a time that ensures the homogeneity of the mixture. f. Optional addition of other additives to this mixture and stirring until homogenization is complete. g. Addition of a catalyst, in particular paratoluenesulphonic acid, to the mixture comprising the total quantity of tannin. h. Stirring the mixture comprising the total quantity of tannin, furfuryl alcohol, diethyl ether, formaldehyde, optionally additives and the catalyst at a speed equivalent to that of step c for a time that ensures the homogeneity of the mixture. ### Claim 16 (depends on 5, 6, 7, 8, 9, 10) Carbonaceous foam capable of being obtained by pyrolysis of a rigid foam according to any one of claims 5 to 10.